WO2016112249A1 - Oxydation de bromure d'hydrogène - Google Patents

Oxydation de bromure d'hydrogène Download PDF

Info

Publication number
WO2016112249A1
WO2016112249A1 PCT/US2016/012579 US2016012579W WO2016112249A1 WO 2016112249 A1 WO2016112249 A1 WO 2016112249A1 US 2016012579 W US2016012579 W US 2016012579W WO 2016112249 A1 WO2016112249 A1 WO 2016112249A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
feeds
cerium
catalyst
hbr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2016/012579
Other languages
English (en)
Other versions
WO2016112249A9 (fr
Inventor
Michael A. BESTOR
Steven A. BIELECKI
Joseph M. O'DAY
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Albemarle Corp
Original Assignee
Albemarle Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Albemarle Corp filed Critical Albemarle Corp
Publication of WO2016112249A1 publication Critical patent/WO2016112249A1/fr
Publication of WO2016112249A9 publication Critical patent/WO2016112249A9/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/09—Bromine; Hydrogen bromide
    • C01B7/096—Bromine

Definitions

  • This invention relates to oxidation of hydrogen bromide to bromine presence of a catalyst.
  • This invention provides processes for oxidation of hydrogen brom elemental bromine by contact with a catalyst at relatively low tempe]
  • conversions greater than 98% have been achieved at thesi conditions.
  • ambient temperatures are suitable when the process is cor under anhydrous conditions.
  • An embodiment of this invention is a process for forming elemental br
  • the process comprises bringing feeds of a gas comprising hydrogen bromide an( comprising molecular oxygen into contact with a catalyst comprising cerium oxide cerium bromide on an inorganic oxide support, characterized in that the catalyst cerium in an amount of about 25 wt% to about 75 wt%, expressed as cerium relative to the total weight of the catalyst, and that the feeds are at a temperature o 200°C or below during process initiation, with the proviso that when the feeds a temperature of about 100°C or below, the feeds are anhydrous during process initiat
  • process initiation and the words “initiating” and “initial reference to the processes of this invention, as used throughout this document, refe: period of time from the beginning of the feeds of the gas comprising hydrogen b and the gas comprising molecular oxygen into the reaction zone until an exotherm in the reaction zone.
  • the exotherm is a significant increase in temperature, typic increase of about 50°C or more.
  • hydrogen bromide is oxidized by mo oxygen, 0 2 , to elemental bromine in the presence of a catalyst; water is a by-produc reaction.
  • the components of the process other than the catalyst are normal preferably in the gas phase at least in the reaction zone.
  • Hydrogen bromide from various sources can be subjected to the processes invention, and the HBr gas does not need to be pure.
  • the HBr gas about 20 mol% or more HBr, more preferably about 50 mol% or more HBr.
  • the HBr gas contains about 20 mol% to about 100 mol%, more pre about 50 mol% to about 100 mol% HBr.
  • the HBr gas can be subjected to the processes of this invention, impurities, such as sulfur-containing compounds, if present in the HBr gas, may afi catalyst, and should be minimized in, or absent from, the HBr gas.
  • impurities such as sulfur-containing compounds
  • anhydrous HBr gas is prefern [0012]
  • the oxidant is molecular oxygen.
  • the molecular oxygen can be in a carrier gas or in a mixture of carrier gases. Suitable carrier gases include helium argon, nitrogen, carbon dioxide, and mixtures thereof; air is an example of a mix carrier gases containing molecular oxygen. Molecular oxygen without a carrier preferred.
  • Suitable catalysts in the practice of this invention include cerium oxide, bromide, and mixtures thereof, on an inorganic oxide support; cerium oxide is pre
  • Inorganic oxide supports include zirconia, hafnia, alumina, titania, yttria, silica, thoi the like, and mixtures thereof.
  • Preferred supports comprise zirconia; more pref zirconia is the only support material.
  • the amount of cerium oxide and/or cerium b on the support is preferably about 25 to about 75 wt% as cerium oxide relative to tl weight of the catalyst, preferably about 30 wt% to about 70 wt% as cerium oxide preferably about 40 to about 70 wt% cerium oxide, and especially with about 6( wt% as cerium oxide, relative to the total weight of the catalyst.
  • the catalyst is cerium oxide on zirconia, with about 25 to about 7: preferably about 30 to about 70 wt%, more preferably about 40 to about 70 wt% oxide, and especially about 60 to 70 wt% cerium oxide relative to the total weighl catalyst.
  • cerium oxide refers amount of cerium on the support, where the numerical value is for cerium oxid ⁇ example, cerium bromide may be used, but the amount of cerium in the catalyst is as the value for cerium oxide.
  • the reaction zone is defined as the area where the HBr gas and the oxy£ come into contact with the catalyst. Both HBr and Br 2 are known to corrode steel presence of water, so it is recommended and preferred that the reaction zone is cons of other materials, such as quartz or ceramic; glass-lined reactors may also be used.
  • the HBr gas and the oxygen gas can be fed in any desired manner.
  • the E and the oxygen gas can be combined at a time before being fed into the reaction the mixture is kept at a relatively low temperature (e.g., about 100°C or 1
  • the HBr gas and the oxygen gas are fed to the reaction zone separate another preferred feeding method, the HBr gas and the oxygen gas are mixed imme prior to being fed into the reaction zone.
  • the oxygen gas is fed in in an amount such that an excess of ; mol% to about 20 mol%, more preferably about 2 mol% to about 10 mol%, stil preferably about 5 mol% to about 10 mol%, of molecular oxygen over the stoichic amount is present in the reaction zone.
  • Feed temperatures refer to both the HBr gas and the oxygen gas. Wr separately, the HBr gas and the oxygen gas are in the desired feed temperature ran HBr gas and the oxygen gas may be at different temperatures, and are preferably same or similar temperatures (e.g. , preferably a difference of about 25°C or less preferably a difference of about 10°C or less).
  • the feed temperature is for the mixture, whk the desired feed temperature range.
  • one or both of the HBr gas and the oxy ⁇ are preferably at one or more temperatures of about 200°C or below during their fi with the proviso that the gas comprising hydrogen bromide and the gas com molecular oxygen are anhydrous when the feed temperature is about 100°C or bel ⁇
  • the processes of this invention are initiated with feeds of HBr the oxygen gas at feed temperatures in the range of about 100°C to about preferably about 100°C to about 175°C, more preferably at about 100°C to about still more preferably at about 100°C to about 125°C, at atmospheric pressure. Anh conditions are not necessary when feeding the HBr gas and the oxygen gas at about or above.
  • the process can be initiated or conducted with the HBr gas and the oxy ⁇ feeds at temperatures of about 100°C or below, and the HBr gas and the oxygen ga can be at temperatures as low as ambient temperatures (e.g. , about 18°C).
  • Pr temperatures when the process is initiated with the HBr gas and the oxygen ga: under anhydrous conditions are in the range of about 18°C to about 150°C preferably about 50°C to about 110°C, and still more preferably about 50°C tc 100°C.
  • Anhydrous conditions mean the absence of water, but it is understoc adventitious amounts of water may be present.
  • Initiating a ] under anhydrous conditions generally means that the HBr gas and the oxygen
  • the feed temperatures for the HBr gas and the oxygen gas refer period of time before an exotherm occurs in the reaction zone
  • the HBr gas and oxygen gas can be fed at their feed temperatures after the exotherm occurs, if desirei
  • the reaction zone or at least a portion thereof can be preheated, although not necessary, because of the exothermicity of the reaction that occurs during the p Preheating is preferred when operating on smaller scales, e.g. , laboratory scales. I initiating the feeds of the HBr gas and the oxygen gas, it is recommended and prefe flush an inert gas (e.g., helium, neon, argon, nitrogen, carbon dioxide, or mixtures two or more of these, preferably nitrogen) through the reaction zone during the preh
  • an inert gas e.g., helium, neon, argon, nitrogen, carbon dioxide, or mixtures two or more of these, preferably nitrogen
  • the preheating is for a period of time at a temperature of about or more, preferably about 125°C to about 250°C, more preferably about 125°C tc 200°C, to remove water from reaction zone before starting the feeds of HBr gas ; oxygen gas into the reaction zone.
  • Heating of the reaction zone is generally not required during the processes invention because the oxidation reaction that occurs in these processes is very exotl
  • the magnitude of the exotherm is large enough that heat transfer from the reaction normally needed to keep the reaction zone at the desired temperature, even when th of HBr gas and the oxygen gas are at ambient temperature.
  • All of the components in the reaction zone other than the catalyst are nc and preferably in the vapor phase. This means that the reactants, HBr and 0 2 , as the products, Br 2 and water, are in the vapor phase while in the reaction zone, minimum, water should be in the vapor phase to prevent condensation of water catalyst. Normally, the heat of reaction is sufficient or more than enough to maint temperature in the reaction zone high enough that all or nearly all of the non-c components remain in the vapor phase.
  • the inorganic support is zirconia
  • the cerium is about 30 wt% to about 70 wt%, preferably about ⁇ to about 70 wt%, more preferably about 60 wt% to about 70 wt%, expressed as oxide, relative to the total weight of the catalyst, and the feeds are at a temperature range of about 100°C to about 175°C during process initiation.
  • the inorganic support is zirconia
  • the cerium is about 30 wt% to about 70 wt%, preferably about ⁇ to about 70 wt%, more preferably about 60 wt% to about 70 wt%, expressed as oxide, relative to the total weight of the catalyst, and the feeds are at a tempera about 100°C or below during process initiation.
  • the processes of this invention produce elemental b and water.
  • the water can be separated from bromine by any convenient mea preferred method is distillation. Another method is to condense the product into a allow it to separate into layers, and draw off the layers separately; the water laye contains some residual elemental bromine, which can be recovered if desired.
  • Elemental bromine produced in the processes of this invention can be recv the process from which the HBr emanated, if applicable.
  • the ele bromine can be used in a different process, or stored for later use.
  • Cerium oxide on zirconia (20 g; 69.5 wt% cerium oxide; Actalys ® ; Rhodi was placed in the quartz tube reactor.
  • the HBr was supplied from a gas cylind molecular oxygen was supplied from a gas cylinder.
  • the quartz tube reactor was preheated at 150°C for 60 minutes with a str nitrogen flushing the quartz tube.
  • Several runs of the reaction were carried out wi the HBr and oxygen feeds at the same selected temperature (100°C, 150°C, or 1 HBr was fed into one gas feed line at a rate of 150 seem (150 cm /min.), and oxyg fed into the other gas feed line at a rate of 50 seem, and the mixture of HBr and ⁇ was fed from the mixing "Y" into the quartz tube reactor.
  • the HBr and oxygen w for 300 minutes. A visible red vapor was seen after only a few seconds of opt
  • Br 2 and water were collected in the two 1-L flasks, the cone column, and the caustic trap. The amount of unreacted HBr was determined on s from the caustic trap by acid-base titration. Results are summarized in Table 1.
  • Example 1 was repeated, using air instead of pure oxygen; the air was f rate of 200 seem.
  • the amount of bromine carried over to the caus was greater than in Example 1 (3% of the b produced). Results are summarized in Table 2.
  • the invention may comprise, consist, or consist essentially of the m and/or procedures recited herein.
  • the term "about” modifying the quantity of an ingredient compositions of the invention or employed in the methods of the invention re variation in the numerical quantity that can occur, for example, through typical me; and liquid handling procedures used for making concentrates or use solutions in t world; through inadvertent error in these procedures; through differences manufacture, source, or purity of the ingredients employed to make the composit carry out the methods; and the like.
  • the term about also encompasses amounts tha due to different equilibrium conditions for a composition resulting from a particulai mixture. Whether or not modified by the term "about”, the claims include equival the quantities.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé permettant de former du brome élémentaire. Le procédé consiste à mettre en contact des charges d'alimentation d'un gaz comprenant du bromure d'hydrogène et d'un gaz comprenant de l'oxygène moléculaire avec un catalyseur comprenant de l'oxyde de cérium et/ou du bromure de cérium sur un support d'oxyde inorganique. Le procédé est caractérisé en ce que le catalyseur contient du cérium en une proportion d'environ 25 % en poids à environ 75 % en poids, exprimée sous la forme d'oxyde de cérium, par rapport au poids total du catalyseur, et en ce que les charges d'alimentation se trouvent à une température inférieure ou égale à environ 200 °C pendant l'initiation du procédé, à condition que, lorsque les charges d'alimentation sont à une température inférieure ou égale à environ 100 °C, les charges d'alimentation sont anhydres pendant l'initiation du procédé.
PCT/US2016/012579 2015-01-09 2016-01-08 Oxydation de bromure d'hydrogène Ceased WO2016112249A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562101426P 2015-01-09 2015-01-09
US62/101,426 2015-01-09

Publications (2)

Publication Number Publication Date
WO2016112249A1 true WO2016112249A1 (fr) 2016-07-14
WO2016112249A9 WO2016112249A9 (fr) 2016-09-01

Family

ID=55642811

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/012579 Ceased WO2016112249A1 (fr) 2015-01-09 2016-01-08 Oxydation de bromure d'hydrogène

Country Status (1)

Country Link
WO (1) WO2016112249A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3310380A (en) * 1964-02-13 1967-03-21 Universal Oil Prod Co Bromine recovery
US3346340A (en) * 1966-08-11 1967-10-10 Universal Oil Prod Co Production of bromine by oxidation of hydrogen bromide
US3353916A (en) * 1966-04-25 1967-11-21 Universal Oil Prod Co Quantitative recovery of bromine by two stage catalytic oxidation of hydrogen bromide
US5366949A (en) * 1992-02-04 1994-11-22 Catalytica, Inc. CeBr3 catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3310380A (en) * 1964-02-13 1967-03-21 Universal Oil Prod Co Bromine recovery
US3353916A (en) * 1966-04-25 1967-11-21 Universal Oil Prod Co Quantitative recovery of bromine by two stage catalytic oxidation of hydrogen bromide
US3346340A (en) * 1966-08-11 1967-10-10 Universal Oil Prod Co Production of bromine by oxidation of hydrogen bromide
US5366949A (en) * 1992-02-04 1994-11-22 Catalytica, Inc. CeBr3 catalyst

Also Published As

Publication number Publication date
WO2016112249A9 (fr) 2016-09-01

Similar Documents

Publication Publication Date Title
CN105037076B (zh) 制备2,3,3,3-四氟丙烯的方法
JP7386233B2 (ja) トリフルオロヨードメタンを生成するためのプロセス
JP5926802B2 (ja) セボフルランの製造方法
JP2004002301A (ja) 一酸化炭素およびメタノールの製造方法
EP0022697B1 (fr) Procédé de préparation directe d'aldéhyde de bêta-méthylthio-propionique
JP5497052B2 (ja) モノニトロベンゼンを製造するための断熱的方法
JPH02266A (ja) トリフルオロメタンスルホニルクロリドの製造方法
JP2013533246A (ja) 高温ラクタム中和
KR20110059707A (ko) 시클릭 케톤의 제조 방법
US9394245B2 (en) Process for sulfonating halobenzene derivatives with sulfur trioxide
TW380132B (en) A process for the preparation and fractionation of a mixture of dimethyl ether and chloromethane with methanol as extractant
WO2016112249A1 (fr) Oxydation de bromure d'hydrogène
AU749982B2 (en) Method for preparing methyl carbazate
ES8207116A1 (es) Procedimiento para la preparacion de esteres de acidos car- boxilicos insaturados
US7919657B2 (en) Process for dehydration of hexafluoroacetone hydrate
TWI605034B (zh) Ｎ－乙烯基羧酸醯胺之製造方法
AU735469B2 (en) Process for the hydroxylation of benzene
US6869582B2 (en) Process for the synthesis of BrSF5
CN106999844A (zh) 从含烃气体混合物中除去氧气
CN109053454A (zh) 一种硝基甲烷的制备方法以及聚(4-乙烯吡啶)的应用
WO2005113430A1 (fr) Processus concurrent d'oxydation du dioxyde de soufre et son utilisation dans la fabrication d'anhydride tétrabromophtalique
US4393257A (en) Process for preparing benzotrifluoride and its derivatives
US4365101A (en) Process for preparing benzotrifluoride and its derivatives
JPS58188836A (ja) イソ酪酸フツ化物もしくはイソ酪酸の製法
US4189602A (en) Acid oxidation process

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16713130

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16713130

Country of ref document: EP

Kind code of ref document: A1